Polymerized oils &amp; methods of manufacturing the same

ABSTRACT

Described herein is a polymerized biorenewable, petroleum based, previously modified, or functionalized oil, comprising a polymeric distribution having about 2 to about 80 wt % oligomer content, a polydispersity index ranging from about 1.0 to about 5.0, and sulfur content ranging from 0.001 wt % to about 8 wt %. Methods of manufacturing the polymerized oil as well as its incorporation into asphalt paving, roofing, and coating applications are also described.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.62/126,064 filed Feb. 27, 2015, which is hereby incorporated byreference in its entirety.

TECHNICAL FIELD

This disclosure relates to polymerized oils and methods for polymerizingoils and blending with asphalt to enhance performance of virgin asphaltand/or pavements containing recycled and aged bituminous material.

BACKGROUND

Recent technical challenges facing the asphalt industry have createdopportunities for the introduction of agriculture-based products for theoverall performance enhancement of asphalt. Such performanceenhancements may include expanding the useful temperature interval (UTI)of asphalt, rejuvenating aged asphalt, and compatibilizing elastomericthermoplastic polymers in asphalt.

SUMMARY

Aspects described herein provide a polymerized oil, comprising apolymeric distribution having about 2 to about 80 wt % oligomer content,a polydispersity index ranging from about 1.0 to about 5.0, and sulfurcontent ranging from 0.001 wt % to about 8 wt %.

Other aspects described herein provide a method of polymerizing an oilcomprising heating a biorenewable, petroleum based, previously modified,or functionalized oil to at least 100° C., adding a sulfur-containingcompound to the heated oil, and allowing the sulfur-containing compoundto react with the oil to produce a polymerized oil comprising apolymeric distribution having about 2 to about 80 wt % oligomer content,a polydispersity index ranging from about 1.0 to about 5.0, and sulfurcontent ranging from 0.001 wt % to about 8 wt %.

Yet other aspects described herein provide the incorporation of thepolymerized oil in asphalt paving, roofing, and coating applications.

DESCRIPTION OF THE FIGURES

FIGS. 1 and 2 show a complex modulus curve of asphalt as a function ofreduced loading frequency.

DETAILED DESCRIPTION

“Flash Point” or “Flash Point Temperature” is a measure of the minimumtemperature at which a material will initially flash with a brief flame.It is measured according to the method of ASTM D-92 using a ClevelandOpen Cup and is reported in degrees Celsius (° C.).

“Oligomer” is defined as a polymer having a number average molecularweight (Mn) larger than 1000. A monomer makes up everything else andincludes monoacylgyclerides (MAG), diacylglycerides (DAG),triacylglycerides (TAG), and free fatty acids (FFA).

“Performance Grade” (PG) is defined as the temperature interval forwhich a specific asphalt product is designed. For example, an asphaltproduct designed to accommodate a high temperature of 64° C. and a lowtemperature of −22° C. has a PG of 64-22. Performance Grade standardsare set by America Association of State Highway and TransportationOfficials (AASHTO) and the American Society for Testing Materials(ASTM).

“Polydispersity Index” (also known as “Molecular Weight Distribution”)is the ratio of weight average molecular weight (Mw) to number averagemolecular weight (Mn). The polydispersity data is collected using a GelPermeation Chromatography instrument equipped with a Waters 510 pump anda 410 differential refractometer. Samples are prepared at an approximate2% concentration in a THF solvent. A flow rate of 1 ml/minute and atemperature of 35° C. are used. The columns consist of a Phenogel 5micron linear/mixed Guard column, and 300×7.8 mm Phenogel 5 microncolumns (styrene-divinylbenzene copolymer) at 50, 100, 1000, and 10000Angstroms. Molecular weights were determined using the followingstandards:

Arcol Epoxidized LHT Soybean Acclaim Multranol Acclaim StandardMonoolein Diolein 240 Triolein Oil 2200 3400 8200 Molecular 356 620 707878 950 2000 3000 8000 Weight (Daltons)

“Useful Temperature Interval” (UTI) is defined as the interval betweenthe highest temperature and lowest temperature for which a specificasphalt product is designed. For example, an asphalt product designed toaccommodate a high temperature of 64° C. and a low temperature of −22°C. has a UTI of 86. For road paving applications, the seasonal andgeographic extremes of temperature will determine the UTI for which anasphalt product must be designed. UTI of asphalt is determined by aseries of AASHTO and ASTM standard tests developed by the StrategicHighway Research Program (SHRP) also known as the “Performance Grading”(PG) specification.

Asphalt and Bituminous Materials

For the purpose of this invention asphalt, asphalt binder, and bitumenrefer to the binder phase of an asphalt pavement. Bituminous materialmay refer to a blend of asphalt binder and other material such asaggregate or filler. The binder used in this invention may be materialacquired from asphalt producing refineries, flux, refinery vacuum towerbottoms, pitch, and other residues of processing of vacuum towerbottoms, as well as oxidized and aged asphalt from recycled bituminousmaterial such as reclaimed asphalt pavement (RAP), and recycled asphaltshingles (RAS).

Starting Oil Material

Biorenewable oils or petroleum based oil may be used as the starting oilmaterial.

Petroleum based oil includes a broad range of hydrocarbon-basedcompositions and refined petroleum products, having a variety ofdifferent chemical compositions which are obtained from recovery andrefining oils of fossil based original and considered non-renewable inthat it takes millions of year to generate crude starting material. Thisalso includes waste/crude streams resulting from petroleum based oilrefining processes.

Biorenewable oils includes oils isolated from plants, animals, andalgae. Examples of plant-based oils may include but are not limited tosoybean oil, linseed oil, canola oil, rapeseed oil, castor oil, talloil, cottonseed oil, sunflower oil, palm oil, peanut oil, safflower oil,corn oil, corn stillage oil, lecithin (phospholipids) and combinationsand crude streams thereof.

Examples of animal-based oils may include but are not limited to animalfat (e.g., lard, tallow) and lecithin (phospholipids), and combinationsand crude streams thereof.

Biorenewable oils can also include partially hydrogenated oils, oilswith conjugated bonds, and bodied oils wherein a heteroatom is notintroduced, for example but not limited to, diacylglycerides,monoacylglycerides, free fatty acids, alkyl esters of fatty acids (e.g.,methyl, ethyl, propyl, and butyl esters), diol and triol esters (e.g.,ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane),and mixtures thereof. An example of biorenewable oils may be wastecooking oil or other used oils.

Previously modified or functionalized oils may also be used as thestarting oil material. Examples of previously modified oils are thosethat have been previously vulcanized or polymerized by otherpolymerizing technologies, such as maleic anhydride or acrylic acidmodified, hydrogenated, dicyclopentadiene modified, conjugated viareaction with iodine, interesterified, or processed to modify acidvalue, hydroxyl number, or other properties. Some examples of previouslymodified oils are polyol esters, for example polyglycerol ester or acastor oil ester, or estolides. Such modified oils can be blended withunmodified plant-based oils or animal-based oils, fatty acids, glycerin,and/or lecithin. Examples of functionalized oils are those wherein aheteroatom (oxygen, nitrogen, sulfur, and phosphorus) has beenintroduced.

Sulfur Crosslinking of the Oil

In the various aspects, polymerization of the biorenewable, petroleumbased, previously modified, or functionalized oil is achieved throughcrosslinking of the fatty acid chains and/or the glyceride fraction ofthe tri-glyceride molecules contained in the biorenewable, petroleumbased, previously modified, or functionalized oil utilizing asulfur-containing compound. The sulfur in the sulfur-containing compoundis preferably in a reduced form. The polymerization method comprises thesteps of (a) heating a biorenewable, petroleum based, previouslymodified, or functionalized oil (b) adding a sulfur-containing compoundto the heated oil, and (c) allowing the sulfur-containing compound toreact with the oil to produce a polymerized oil with a desired polymericdistribution (having about 2 wt % to about 80 wt % oligomer content),polydispersity index (from about 1.0 to about 5.0), and sulfur content(between about 0.01 wt % and about 8 wt %).

In a first step, the biorenewable, petroleum based, previously modified,or functionalized oil is heated in a vessel equipped with an agitator toat least 100° C. In more preferred aspects, the biorenewable, petroleumbased, previously modified, or functionalized oil (may also becollectively referred to herein as the “oil”) is heated to at least 115°C. In preferred aspects, the sulfur-containing compound is graduallyadded to the heated biorenewable, petroleum based, previously modified,or functionalized oil and may be added in either a solid or a moltenform, however it shall be understood that the sulfur-containing compoundmay be added before the oil or simultaneously with the oil. Inpreferable aspects, the sulfur-containing compound may be elementalsulfur, but is not limited to such. The reaction between the sulfur andoil inherently increases the temperature of the oil-sulfur mixture andin preferred aspects, the reaction is held at temperatures between about130° C. and about 250° C., more preferably between about 130° C. andabout 220° C., and even more preferably between about 160° C. and about200° C. during the course of the reaction.

The oil-sulfur mixture may be continuously sparged with a gas-containingstream during the polymerization reaction between the oil and thesulfur. The gas-containing stream may be selected from the groupconsisting of nitrogen, air, and other gases. The gas-containing streammay help facilitate the reaction and may also assist in reducing odors(H₂S and other sulfides) associated with the reaction, in the finalproduct. Use of air can be beneficial, as it may lead tooxi-polymerization of the oil in addition to the sulfurization process.

Optionally, accelerators may be used to increase the rate of thereaction. Examples of accelerators include, but are not limited to, zincoxide, magnesium oxide, dithiocarbamates.

The reaction may continue and may be continuously monitored using gelpermeation chromatography (GPC) and/or viscosity until the desireddegree of polymerization is achieved as discussed below.

The robustness of the sulfur crosslinking reaction and the ability touse it for the polymerization of lower cost feedstocks containing a highfree fatty acid content and residual moisture is an advantage of thispolymerization method compared to other processes, providing flexibilityin starting material selection.

Polymerization Characteristics

The reaction between the sulfur-containing compound and thebiorenewable, petroleum based, previously modified, or functionalizedoil is driven until a polymeric distribution having between about 2 wt %and about 80 wt % oligomers (20 wt % to 98 wt % monomers), and morepreferably between about 15 wt % to about 60 wt % oligomers (40 wt % to85 wt % monomers), and even more preferably between about 20 wt % toabout 60 wt % oligomers (40 wt % to 80 wt % monomers) is achieved. Ineven more preferred aspects, the polymeric distribution ranges fromabout 50 wt % to about 75 wt % oligomers and about 25 wt % to about 50wt % monomers.

The polydispersity index of the polymerized oil ranges from about 1.0 toabout 5.0, more preferably from about 1.30 to about 2.20, and even morepreferably from about 1.50 to about 2.05.

A benefit of the reaction described herein is the low sulfur content inthe resulting polymerized oil. In some aspects, the sulfur content makesup less than 8 wt % of the polymerized oil. In other aspects, the sulfurcontent makes up less than 6 wt % of the polymerized oil. In yet otheraspects, the sulfur content makes up less than 4 wt % of the polymerizedoil. And in other aspects, the sulfur content makes up less than 2 wt %of the polymerized oil. The sulfur content, however, comprises at least0.001 wt % of the polymerized oil.

The flash point of the resulting polymerized oil, as measured using theCleveland Open Cup method, is at least about 100° C. and no more thanabout 400° C. In some aspects, the flash point of the polymerized oil isbetween about 200° C. and about 350° C. In other aspects, the flashpoint of the polymerized oil is between about 220° C. and about 300° C.In yet other aspects, the flash point of the polymerized oil is betweenabout 245° C. and about 275° C. The polymerized oils described hereinmay have higher flash point than its starting oil material, especiallywhen compared against other polymerization techniques.

The viscosity of the polymerized oil will vary based on the type ofstarting oil material, but generally ranges from about 1 cSt to about100 cSt at 100° C.

End-Use Applications

In one aspect, the present invention provides a modified asphaltcomprising a blend of 60 wt % to 99.9 wt % of asphalt binder and 0.1 wt% to 40 wt % of the polymerized oil, and a method for making the same,in which polymerization of the oil is achieved through sulfurcross-linking as described above. The modified asphalt may be used forroad paving or roofing applications.

In another aspect, the present invention provides a modified asphaltcomprising a blend of 60 wt % to 99.9 wt % asphalt binder and 0.1 wt %to 40 wt % of the polymerized oil, and a method for making the same,wherein the polymerized oil is a blend of an polymerized petroleum basedoil achieved through sulfur cross-linking, as described above, and oneor more of the biorenewable, petroleum based, previously modified orfunctionalized oils described above, for example: unmodified plant-basedoil, animal-based oil, fatty acids, fatty acid methyl esters, gums orlecithin, and gums or lecithin in modified oil or other oil or fattyacid.

Other components, in addition to the polymerized oil, may be combinedwith an asphalt binder to produce a modified asphalt, for example butnot limited to, thermoplastic elastomeric and plastomeric polymers(styrene-butadiene-styrene, ethylene vinyl-acetate, functionalizedpolyolefins, etc.), polyphosphoric acid, anti-stripping additives(amine-based, phosphate-based, etc.), warm mix additives, emulsifiersand/or fibers. Typically, these components are added to the asphaltbinder/polymerized oil at doses ranging from about 0.1 wt % to about 10wt %.

Asphalt Modification

The declining quality of bitumen drives the need for adding chemicalmodifiers to enhance the quality of asphalt products. Heavy mineral oilsfrom petroleum refining are the most commonly used modifiers. Thesemineral oils extend the low temperature limit of the asphalt product by‘plasticizing’ the binder, however this also tends to lower the uppertemperature limit of the asphalt.

Mineral flux oils, petroleum-based crude distillates, and re-refinedmineral oils have been used in attempts to soften the asphalt. Often,use of such material results in a decrease of the high temperaturemodulus of asphalt more than the low temperature, making the asphaltmore prone to rutting at high temperatures. Such effects result in thereduction of the Useful Temperature Interval (UTI).

Mineral flux oils, petroleum-based crude distillates, and re-refinedmineral oils often have volatile fractions at pavement constructiontemperatures (e.g., 150 to 180° C.), generally have lower flashpointsthan that of asphalt, and may be prone to higher loss of performance dueto oxidative aging.

The polymerized oils and blends described herein are not only viablesubstitutes for mineral oil, but have also been shown to extend the UTIof asphalts to a greater degree than other performance modifiers,therefore providing substantial value to asphalt manufacturers. Theobserved increase in UTI using the polymerized oils described herein isa unique property not seen in other asphalt softening additives such asasphalt flux, fuel oils, or flush oils. Typically one grade improvementin either the SHRP Performance Grading (PG) specification or thePenetration grading system used in many countries is achieved withapproximately 2 to 3 wt % of the polymerized oil by weight of theasphalt. For example, the increase in UTI seen for approximately 3% byweight addition of the polymerized oil can be as much as 4° C.,therefore providing a broader PG modification range such that the lowerend temperature can be lower without sacrificing the higher endtemperature.

Rejuvenation of Aged Bituminous Material

Asphalt “ages” through a combination of mechanisms, mainly oxidation andvolatilization. Aging increases asphalt modulus, decreases viscousdissipation and stress relaxation, and increases brittleness at lowerperformance temperatures. As a result, the asphalt becomes moresusceptible to cracking and damage accumulation. The increasing usage ofrecycled and reclaimed bituminous materials which contain highly agedasphalt binder from sources such as reclaimed asphalt pavements (RAP)and recycled asphalt shingles (RAS) have created a necessity for“rejuvenators” capable of partially or completely restoring therheological and fracture properties of the aged asphalt. Aging ofasphalt has also been shown to increase colloidal instability and phaseincompatibility, by increasing the content of high molecular weight andhighly polar insoluble “asphaltene” fraction which may increasinglyassociate. The use of the polymerized oil described herein areparticularly useful for RAP and RAS applications. The polymerized oildescribed in this document act as a compatibilizer of the asphaltfractions, especially in aged and oxidized asphalt, resulting in abalanced and stable asphalt binder with restored performance anddurability.

During plant production the asphalt is exposed to high temperatures(usually between 150 to 190° C.) and exposure to air during whichsignificant oxidation and volatilization of lighter fractions can occurleading to an increase in modulus and a decrease in viscous behavior.The aging process is simulated using a Rolling Thin Film Oven (ASTMD2872) during which a rolling thin film of asphalt is subjected a jet ofheated air at about 163° C. for about 85 minutes. The rheologicalproperties are measured before and after the aging procedure using aDynamic Shear Rheometer following ASTM D7175 using the ratio of the|G*|/sin δ after to before aging, in which G* is the complex modulus andδ is the phase angle. The larger the ratio of the (|G*|/sin δ) afteraging to the (|G*|/sin δ) before aging, the higher the effect ofoxidative aging and volatilization on the tested asphalt.

Using this procedure it is shown that asphalts treated with thepolymerized oil or blends thereof described in this invention have alower ratio, thus showing a lower tendency for change in rheologicalproperties as a result of oxidative aging and volatilization.

Accordingly, the polymerized oils described herein have been shown to becapable of rejuvenating aged asphalt binder, and modify the rheologicalproperties of a lesser aged asphalt binder. As a result, small dosagesof the polymerized oil can be used to incorporate high content of agedrecycled asphalt material into pavements and other applicationsresulting in significant economic saving and possible reduction in theenvironmental impact of the pavement through reduction of use of freshresources.

Notably, the polymerized oils described herein may be used to make anemulsion for use in asphalt rejuvenation applications. The emulsioncomprises an oil phase and an aqueous phase. The oil phase comprises thepolymerized oil described herein and may further comprise of asphaltbinder and other additives and modifiers, wherein the oil is about 0.1to 100 wt % of the oil phase. The aqueous phase often comprises asurfactant and may further comprise natural and synthetic polymers (suchas Styrene Butadiene Rubber and latex) and/or water phase thickeners.

The oil phase makes up about 15 to 85 wt % of the emulsion with theaqueous phase making up the remaining balance. It is understood by thoseskilled in the art that emulsions are sometimes further diluted withwater at time of application, thus the effective oil phase content ofthe diluted emulsion may be reduced indefinitely.

Further contemplated herein is a method comprising applying the emulsionto the surface of an existing pavement or applying the emulsion to treatRAS or RAP and further mixing the treated RAS or RAP with virgin asphaltthereby obtaining a rejuvenated asphalt blend.

The emulsion may also be used as part of a cold patching material, ahigh performance cold patch or cold mix application that containsrecycled asphalt thereby obtaining treated RAS or RAP.

In other aspects, the emulsion may be used for cold-in-place recyclingof milled asphalt pavements or hot-in-place recycling of milled asphaltpavements.

Elastomeric Thermoplastic Polymer Compalibilizalion in Asphalt

Asphalt is often modified with thermoplastic elastomeric and plastomericpolymers such as Styrene-Butadiene-Styrene (SBS) to increase hightemperature modulus and elasticity, to increase resistance to heavytraffic loading and toughening the asphalt matrix against damageaccumulation through repetitive loading. Such polymers are usually usedat 3 to 7 wt % dosages in the asphalt and high shear blended intoasphalt at temperatures exceeding 180° C. and allowed to “cure” atsimilar temperatures during which the polymer swells by adsorption oflighter fractions in the asphalt until a continuous volume phase isachieved in the asphalt.

The volume phase of the fully cured polymer will be affected by degreeof compatibility of the polymer in the asphalt and the fineness of thedispersed particles, resulting in an increased specific area andenhanced swelling potential through increase of the interface surfacebetween asphalt and polymer.

The polymerized oils described in this document have been shown to becapable of further compatibilizing elastomeric polymer in the asphalt,when the oil is added and blended into the asphalt before theincorporation of the polymer, or the curing stage. This will beespecially effective in asphalt binders that are not very compatiblewith the elastomeric polymer. Furthermore, the oil may contribute to thelighter fractions that swell the polymers during the curing period.

Warm Mix Additives and Asphalt

In recent years an increasing portion of pavements are produced usingwhat is commonly referred to as “warm mix additives” to produce “warmmix” asphalt pavements. Warm mix pavements can be produced and compactedat lower production temperatures, require less compaction effort toachieve target mixture density, and as a result can retain theproperties necessary for compaction at lower temperature enabling anincrease in the maximum haul distance of the asphalt mixture from theplant to the job site.

The different mechanisms through which warm mix additives provide abenefit include increased lubrication of aggregates during asphaltmixture compaction, reduction of the binder viscosity at productiontemperatures, and better coating and wettability of the aggregates. Thusa diverse range of chemicals and additives may exhibit one or more ofthe properties attributed to warm mix additives when added to an asphaltmixture.

The polymerized oils described herein can be used as a warm mix additiveand/or compaction aid, to achieve a number of the benefits expected froma warm mix additive, including minimum decreasing production andconstruction temperatures through increase in aggregate lubrication andaggregate wettability. In such an application the additive would be usedat dosages preferably in the range of between about 0.1 and 2% by weightof the bitumen.

EXAMPLES

The following examples are presented to illustrate the present inventionand to assist one of ordinary skill in making and using same. Theexamples are not intended in any way to otherwise limit the scope of theinvention.

Experimental Method

A charge of precipitated sulfur (mass ranges between 6.5 grams to 56.5grams) is added to a 1 liter round bottom flask containing 650 grams ofvegetable oil. The reactor is then heated to the target reactiontemperature using a heating mantle, taking care not to over shoot thetarget temperature by more than 5° C. The reaction mixture is agitatedusing a motorized stirrer with a stir shaft and blade. The reaction iscontinuously sparged with nitrogen at 2-12 standard cubic feet per hour(SCFH). A condenser and receiving flask is used to collect anydistillate.

It is noted that the reaction will create foam around 110-115° C. whenthe sulfur melts into the oil. The reaction is monitored using GPC, tomeasure the oligomer content and distribution, and viscosity is measuredat 40° C. using ASTM D445. The reaction is considered complete when thedesired oligomer content has been achieved. The reactor is then cooledto 60° C.

EXAMPLES

The following examples are presented to illustrate the present inventionand to assist one of ordinary skill in making and using same. Theexamples are not intended in any way to otherwise limit the scope of theinvention.

Experimental Method

A charge of precipitated sulfur (mass ranges between 6.5 grams to 56.5grams) is added to a 1 liter round bottom flask containing 650 grams ofvegetable oil. The reactor is then heated to the target reactiontemperature using a heating mantle, taking care not to over shoot thetarget temperature by more than 5° C. The reaction mixture is agitatedusing a motorized stirrer with a stir shaft and blade. The reaction iscontinuously sparged with nitrogen at 2-12 standard cubic feet per hour(SCFH). A condenser and receiving flask is used to collect anydistillate.

It is noted that the reaction will create foam around 110-115° C. whenthe sulfur melts into the oil. The reaction is monitored using GPC, tomeasure the oligomer content and distribution, and viscosity is measuredat 40° C. using ASTM D445. The reaction is considered complete when thedesired oligomer content has been achieved. The reactor is then cooledto 60° C.

Example 1: Asphalt Modified with Polymerized Palm Oil #1

A modified asphalt binder comprising:

-   -   97.0% by weight of neat (i.e., unmodified) asphalt binder graded        at a standard grade of PG64-22 (and “true” grade of PG        64.88-24.7) Note: the true grade represents the exact        temperatures at which the asphalt met the controlling        specification values, which will always meet and exceed that of        the corresponding standard grade (i.e. the true high temperature        grade will always be larger than the standard high temperature        grade, and the true low temperature grade will always be lower        than that of the standard low temperature grade).    -   3.0% by weight of sulfurized refined palm oil reacted with 3% by        weight of elemental sulfur at 160° C. for 5 hrs under a Nitrogen        sparge. This resulted in a modifier with:        -   31.8% oligomers        -   Viscosity of 17.2 cSt at 100° C.        -   Polydispersity Index (PDI) of approximately 1.30

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance with AASHTO M320. The modification resulted in a 4.8° C.low temperature grade improvement, taking the neat binder grade of PG64-22 to a PG 58-28. The net change in the high and low performancegrade resulted in a Useful Temperature Interval improved by 0.8° C.Details are shown Table 1.

TABLE 1 S- UTI¹ O-DSR² R-DSR³ BBR⁴ m-BBR⁵ Binder Name ° C. ° C. ° C. °C. ° C. Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized 90.460.04 60.72 −30.4 −32.7 Refined Palm Oil #1 ¹UTI: Useful TemperatureInterval, as the difference between the high temperature performancegrade and the low temperature performance grade, as determined usingAASHTO M320. ²O-DSR: The High Temperature Performance Grade of theUnaged (“Original”) asphalt binder as measured using a Dynamic ShearRheometer (DSR) following ASTM D7175 and AASHTO M320. ³R-DSR: The HighTemperature Performance Grade of the Rolling Thin Film Oven Aged (RTFO,following ASTM D2872) asphalt binder as measured using a Dynamic ShearRheometer (DSR) following ASTM D7175 and AASHTO M320. ⁴S-BBR: The LowTemperature Performance Grade controlled by the Creep Stiffnessparameter (“S”), as measured on an asphalt binder conditioned using boththe Rolling Thin Film Oven (ASTM D2872) and Pressure Aging Vessel (ASTMD6521), using a Bending Beam Rheometer following ASTM D6648 and AASHTOM320. ⁵m-BBR: The Low Temperature Performance Grade controlled by theCreep Rate parameter (“m” value), as measured on an asphalt binderconditioned using both the Rolling Thin Film Oven (ASTM D2872) andPressure Aging Vessel (ASTM D6521), using a Bending Beam Rheometerfollowing ASTM D6648 and AASHTO M320.

Example 2: Asphalt Modified with Polymerized Palm Oil #2

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of sulfurized refined palm oil reacted with 4% by        weight of elemental sulfur at 160° C. for 20.5 hrs under a        Nitrogen sparge. This resulted in a modifier with:        -   56.18% oligomers        -   Viscosity of 25.0 cSt at 100° C.        -   PDI of approximately 1.50

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 5.9° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval improved by 1.5° C. Detailsare shown in Table 2.

TABLE 2 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized 91.1 60.54 61.13−30.6 −34.1 Refined Palm Oil #2

Example 3: Asphalt Modified with Sulfurized Recovered Corn Oil #1

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of sulfurized recovered corn oil (RCO) reacted        with 1.5% by weight of elemental sulfur at 160° C. for 7 hrs        under a Nitrogen sparge. This resulted in a modifier with:        -   16.0% oligomers        -   PDI of approximately 1.50

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 6.0° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval improved by 0.4° C. Detailsare shown in Table 3.

TABLE 3 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized RCO 1 90.0 59.2860.34 −30.7 −33.6

Example 4: Asphalt Modified with Sulfurized Recovered Corn Oil #2

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of sulfurized recovered corn oil (RCO) reacted        with 6.0% by weight of elemental sulfur at 160° C. for 6 hrs        under a Nitrogen sparge. This resulted in a modifier with:        -   50.3% oligomers        -   Viscosity at 40° C. was 270 cSt        -   PDI of approximately 2.19

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 4.4° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval improved by 0.7° C. Detailsare shown in Table 4.

TABLE 4 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized 90.3 61.23 61.3−29.1 −30.9 RCO 2

Example 5: Asphalt Modified with Sulfurized Refined Sunflower Oil Blend#1

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   14.5% by weight of a sulfurized refined sun flower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomers        -   85.5% by weight of refined sunflower oil        -   Blend of the sulfurized oil and the unmodified oil had 11.9%            oligomer content, a viscosity of 55 cSt at 40° C., and a PDI            of approximately 1.64.

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 5.3° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a full low temperature grade improvement with no change inthe Useful Temperature Interval. Details are shown in Table 5.

TABLE 5 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized Sun 89.6 59.5560.40 −30.0 −30.3 Flower Oil Blend 1

Example 6: Asphalt Modified with Sulfurized Refined Sunflower Oil Blend#2

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   53.9% by weight of a sulfurized refined sunflower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomers        -   46.1% by weight of refined sunflower oil        -   Blend of the sulfurized oil and the unmodified oil had            42.76% oligomer content, a viscosity of 177 Cst at 40° C.,            and a PDI of approximately 3.16.

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. The modification resulted in a 4.8° C.low temperature grade improvement, taking the neat binder grade of PG64-22 to a PG 58-28. Performance grade tests were performed inaccordance to AASHTO M320. The net change in the high and lowperformance grade resulted in a Useful Temperature Interval improved by0.1° C. Details are shown in Table 6:

TABLE 6 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized Sun 89.7 60.2461.25 −29.5 −34.2 Flower Oil Blend 2

Example 7: Asphalt Modified with Sulfurized Refined Sunflower Oil Blend#3

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   63.4% by weight of a sulfurized refined sunflower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomers        -   36.6% by weight of refined sunflower oil        -   Blend of the sulfurized oil and the unmodified oil had 48.3%            oligomer content, a viscosity of 254 Cst at 40° C., and a            PDI of approximately 3.55.

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 5° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval improved by 0.8° C. Detailsare shown in Table.

TABLE 7 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized Sun 90.4 60.7061.64 −29.7 −34.7 Flower Oil Blend 3

Example 8: Asphalt Modified with Refined Sunflower Oil Blend with PalmOil #1

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   14.5% by weight of a sulfurized refined sunflower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomers        -   84.5% by weight of palm oil        -   Blend of the sulfurized oil and the palm oil had about 11.9%            oligomer content        -   PDI of approximately 1.77

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 5° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval slightly decreased by 0.2° C.Details are shown in Table.

TABLE 8 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized SFO-Palm 89.459.65 60.58 −29.7 −30.1 Oil Blend 1

Example 9: Asphalt Modified with Sulfurized Refined Sunflower Oil Blendwith Palm Oil #2

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   59.0% by weight of a sulfurized refined sunflower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomer        -   41.0% by weight of palm oil        -   Blend of the sulfurized oil and the palm oil had about 43%            oligomer content, and a PDI of approximately 2.37

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 4.2° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval slightly decreased by 0.1° C.Details are shown in Table.

TABLE 9 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized SFO-Palm 89.560.62 61.24 −28.9 −33.1 Oil Blend 2

Example 10: Asphalt Modified with Sulfurized Soy Acid Oil (Also Known as“Acidulated Soap Stock”)

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a sulfurized refined Soy Acid Oil reacted with        5.0% by weight of elemental sulfur at 160° C. for 8 hrs under a        Nitrogen sparge. This resulted in a modifier with 28.14%        oligomer, a viscosity of 167 cSt at 40° C., and a PDI of        approximately 2.36. The modifier was blended into the asphalt        after the binder had been annealed at 150° C. for 1 hour.        Performance grade tests were performed in accordance to AASHTO        M320. The modification resulted in a 3.3° C. low temperature        grade improvement, taking the neat binder grade of PG 64-22 to a        PG 58-28. The net change in the high and low performance grade        resulted in a Useful Temperature Interval decreased by 1.5° C.        This example highlights the potential undesirable effect of the        free fatty acid content on the modifier's performance, as it is        significantly less effective in improving the low temperature        performance grade compared to the drop caused at the high        temperature grade. Details are shown in Table 10.

TABLE 10 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. °C. Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized Soy Acid 88.160.07 61.39 −28 −31.6 Oil

Example 11: Asphalt Modified with StyreneButadieneStyrene and SulfurizedRecovered Corn Oil #1 as a Compatabilizer

A modified asphalt binder comprising:

-   -   92.41% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   5.5% by weight of Linear StyreneButadieneStyrene (SBS)    -   0.09% by weight of Elemental Sulfur (used as an SBS cross linker        in the asphalt binder    -   2.0% by weight of sulfurized recovered corn oil (RCO) as        described in Example #3. Blending Procedure:

-   1. The modifier was blended into the asphalt after the binder had    been annealed at 150° C. for 1 hour. The modified binder heated to    about 193° C. for polymer modification.

-   2. The RPM in the high shear mixer was set to 1000 while the SBS was    added (within 1 minute). Immediately after addition of the polymer    the RPM was briefly ramped up to 3000 rpm for approximately 10    minutes to insure full break down of the SBS pellets, after which    the shear level was lowered to 1000 rpm.

-   3. Polymer blending was continued at 1000 rpm for a total of 2 hrs.

-   4. Temperature was dropped to about 182° C. at a 150 rpm at which    point the sulfur cross linker was added.

-   5. Blending was continued at 182° C. and 150 rpm for 2 hrs.

-   6. Polymerized binder was placed in an oven at 150° C. for    approximately 12-15 hrs (overnight) to achieve full swelling of the    polymer.

Performance grade tests were performed in accordance to AASHTO M320.Multiple Stress Creep and Recovery tests were performed on the unagedbinder at 76° C. and on the RTFO residue at 64° C. in accordance toAASHTO T350. The results show that despite the reduction in modulus theaverage percent of recovery of the binder increased for the bindercontaining the modifier, indicating the effect of the modifier as acompatibilizer of SBS, resulting in a better distribution of the samemass of the elastomeric polymer compared to the binder that did notcontain the modifier and consequently a more efficient elastic network.Details are shown in Table 6.

TABLE 6 MSCR at 3.2 kPa MSCR at 3.2 kPa DSR |G*|/sinδ Recovery at 64° C.Recovery at 76° C. Unaged (RTFO) (Unaged) Binder Name 70° C. 76° C. 82°C. (%) (%) +5.5% SBS + 0.09% Sulfur 4.05 2.51 1.62 89.0% 67.7% +2%Example#1 + 5.5% 3.34 2.11 1.40 93.1% 70.0% SBS + 0.09% Sulfur

Example 12: Rejuvenation of Highly Aged Asphalt Binder Using the Oil ofExample #3

The example shown in FIG. 1 shows a complex modulus (G*) curve ofasphalt as a function of reduced loading frequency, measured using aDynamic Shear Rheometer (DSR) following ASTM D7175. The measurementswere made for samples of the asphalt binder used in Example #3 (PG64-22)after laboratory aging to three levels:

-   -   Aging Level 1: 85 minutes of oxidative aging in Rolling Thin        Film Oven at 163° C. (following ASTM D2872).    -   Aging Level 2: Continued aging of samples after aging level 1 by        subjecting it to 20 hrs of oxidative aging at 2.1 MPa air        pressure at 100° C. using a Pressure Aging Vessel (following        ASTM D6521). According to the Performance Grading specification,        20 hrs of PAV aging accelerates the simulated aging that would        normally occur during the performance life of an asphalt        pavement.    -   Aging Level 3: Continued aging of samples after aging level 1        and 2 by subjecting it to an additional 20 hrs of oxidative        aging using a Pressure Aging Vessel (PAV) for a total of 40 hrs        of PAV aging, representing the aging level of a binder from a        severely aged pavement.

FIG. 1 shows that additional aging from level 1 to level 2, and level 2to level 3 caused significant increase in complex modulus across thereduced frequency spectrum.

The asphalt binder at Aging Level 3 was “rejuvenated” by heating thebinder to 150° C. for 1 hr and blending in 5% by weight of the totalbinder of the Example #3 oil. The curve corresponding to the rejuvenatedbinder in FIG. 1 shows that the rejuvenation significantly decreased theG* of the aged asphalt across the whole spectrum of reduced frequencies,resulting in a binder with the rheological properties of a significantlylower aged asphalt binder.

Example 13: Rejuvenation of Highly Aged Asphalt Binder Using the Oil ofExample #4

The example shown in FIG. 1 shows a complex modulus (G*) curve ofasphalt as a function of reduced loading frequency, measured using aDynamic Shear Rheometer (DSR) following ASTM D7175. The measurementswere made for samples of the asphalt binder used in Example #3 (PG64-22)after laboratory aging to three levels described in Example 12, asbefore, showing that additional aging caused significant increase incomplex modulus across the reduced frequency spectrum.

The asphalt binder at Aging Level 3 was “rejuvenated” by heating thebinder to 150° C. for 1 hr and blending in 5% by weight of the totalbinder of the Example #4 oil. The curve corresponding to the rejuvenatedbinder in FIG. 2 shows that the rejuvenation significantly decreased theG* of the aged asphalt across the whole spectrum of reduced frequencies,resulting in a binder with the rheological properties of a lower agedasphalt binder.

Example 14: Effect of Oligomer Content on Improving Aging Stability

A set of samples were prepared in which different dosages of Oleic acid(C18:1) was blended into a refined soybean oil. A set of modifiedasphalt binder comprising the following was made:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (PG        64.9-24.7)    -   3% of modifier, consisting of different proportions of the        following components:        -   Sulfurized Recovered Corn Oil, using 8% sulfur reacted at            160° C. for 4 hrs, achieving a oligomer content of 59.42%            and a PDI of 1.71.        -   Recovered corn oil, used as blend stock with the sulfurized            RCO to make modified oils consisting of 33.76, 39.84, 45.77,            and 50.88% oligomer content.

The modifier blended into the asphalt after the binder had been annealedat 150° C. for 1 hour.

Short term aging was performed using a Rolling Thin Film oven (RTFO) at163° C. for 85 minutes in accordance to ASTM D2872. The procedure isused to simulate the oxidation and volatilization that occurs in theasphalt terminal when the binder is heated and applied to the aggregate.The RTFO conditioning increases the complex modulus through oxidationand volatilization, as measured using the Dynamic Shear Rheometerparallel plate geometry (25 mm diameter, 1 mm gap) in accordance to ASTMD7175.

The results shown in Table 12 demonstrate a significant decrease in theratio of |G*|/sin δ after aging to that before aging, indicating a loweramount of “age hardening” in the asphalt binder as the sulfurizedoligomer content increased. These results indicate the desirability ofincreasing the oligomer content to achieve modified asphalt with higheroxidative aging stability.

TABLE 72 Oligomer Unaged RTFO Aged Ratio of Aging Content |G*|/sinδ at|G*|/sinδ at 58° C. RTFO/ Increase in (%) 58° C. (kPa.) (kPa) Unaged|G*|/sinδ    0% 1.07 2.87 2.67 157.2% 33.76% 1.26 3.31 2.62 153.0%39.84% 1.31 3.31 2.52 145.4% 45.77% 1.36 3.36 2.48 138.1% 59.42% 1.493.31 2.14 113.6%

Example 15: High Temperature Storage and Thermal Stability

To assess the effect of using sulfurized oils on improving theresistance of the asphalt to excessive age hardening at hightemperatures, a simple experiment was devised in which two sets ofasphalt binders were kept in a closed lid container in a 165° C. ovenfor 35 days. The following samples were compared:

Sample 1: A neat asphalt binder graded as PG58-28.Sample 2: A modified binder consisting of:

-   -   97% by weight of the aforementioned PG58-28 neat binder    -   3% by weight of a blend having:        -   59.0% by weight of a sulfurized soybean oil reacted with            7.0% by weight of elemental sulfur at 160° C. for 19 hrs            under a Nitrogen sparge. This resulted in a modifier with            70.8% oligomer        -   41.0% by weight of straight soybean oil        -   Blend of the sulfurized oil and the soybean oil had about            45.6% oligomer content and a PDI of approximately 3.95.            The modifier was blended into the asphalt after the binder            had been annealed at 150° C. for 1 hour.

The content of the cans was blended with a spatula daily and sampledperiodically to be tested using a Dynamic Shear Rheometer. The resultsare shown in Table 13. The results show that both samples age hardenedover time at a relatively similar rate up until 20 days of conditioning.After 20 days the neat asphalt continued to age harden at an acceleratedrate while the asphalt containing the polymerized oil age hardened at amuch lower rate.

The results highlight the use of the polymerized oils described in thisinvention for improving the high temperature thermal and oxidativestability of asphalt. This is of significant value, especially with theincreasing need to store modified asphalt at higher temperatures and thedesirability of minimizing the change properties during storage.

TABLE 13 Material Days in Oven at 165° C. Description 0 d 2 d 6 d 7 d 10d 20 d 27 d 35 d Neat Asphalt |G*|/sinδ at 64° C. 0.62 0.88 0.91 1.121.53 2.61 4.20 12.52 Δ|G*|/sinδ (compared to 0 0.255 0.289 0.493 0.9031.983 3.572 11.897 day 0) Asphalt + 3% |G*|/sinδ at 64° C. 0.39 0.410.82 1.02 1.27 2.32 3.00 5.21 Polymerized Oil Δ|G*|/sinδ (compared to 00.015 0.426 0.630 0.879 1.922 2.607 4.813 day 0)

1. A polymerized petroleum based oil comprising: (a) a polymericdistribution having about 2 to about 80 wt % oligomer content; (b) apolydispersity index ranging from about 1.0 to about 5.0; and (c) sulfurcontent ranging from 0.001 wt % to about 8 wt %.
 2. The polymerizedpetroleum based oil of claim 1, wherein the polymeric distribution hasabout 15 to about 60 wt % oligomer content.
 3. The polymerized petroleumbased oil of claim 1, wherein the polydispersity index ranges from about1.30 to about 2.20.
 4. The polymerized petroleum based oil of claim 1,wherein the sulfur content is less than about 6 wt %.
 5. The polymerizedpetroleum based oil of claim 1, wherein the sulfur content is less thanabout 4 wt %.
 6. The polymerized petroleum based oil of claim 1, whereinthe sulfur content is less than about 2 wt %.
 7. The polymerizedpetroleum based oil of claim 1, having a flash point ranging from about100° C. to about 400° C.
 8. The polymerized petroleum based oil of claim1, having a flash point ranging from about 200° C. to about 350° C. 9.The polymerized petroleum based oil of claim 1, having a flash pointranging from about 245° C. to about 275° C.
 10. A modified asphaltcomprising the polymerized petroleum based oil of claim
 1. 11. Amodified asphalt for use in compositions for paving roads comprising thepolymerized petroleum based oil of claim
 1. 12. A modified asphalt foruse in compositions for roofing materials comprising the polymerizedpetroleum based oil of claim
 1. 13. A rejuvenator for use in asphaltcomprising the polymerized petroleum based oil of claim
 1. 14. Aperformance grade modifier for use in asphalt comprising the polymerizedpetroleum based oil of claim
 1. 15. A compatibilizer for use in asphaltcomprising the polymerized petroleum based oil of claim
 1. 16. Thepolymerized oil of claim 1, further comprising at least one from thegroup consisting of thermoplastic elastomeric and plastomeric polymers,polyphosphoric acid, anti-stripping additives, warm mix additives, andfibers. 17.-40. (canceled)
 41. A modified asphalt, comprising: (a) about60 to about 99.9 wt % asphalt binder; and (b) about 0.1 to about 40 wt %polymerized petroleum based oil comprising i. a polymeric distributionhaving about 2 to about 80 wt % oligomer content; ii. a polydispersityindex ranging from about 1.0 to about 5.0; and iii. sulfur content lessthan about 8 wt %. 42.-44. (canceled)
 45. The modified asphalt of claim41, further comprising at least one from the group consisting ofthermoplastic elastomeric and plastomeric polymers, polyphosphoric acid,anti-stripping additives, warm mix additives, emulsifier, and fibers.46. A modified asphalt, comprising: (a) about 60 to about 99.9 wt %asphalt binder; and (b) about 0.1 to about 40 wt % of a blend ofpolymerized petroleum based oil and unmodified biorenewable oil,petroleum based oil, previously modified or functionalized oil, whereinthe polymerized petroleum based oil has a i. a polymeric distributionhaving about 2 to about 80 wt % oligomer content; ii. a polydispersityindex ranging from about 1.0 to about 5.0; and iii. sulfur content lessthan about 8 wt %.
 47. The modified asphalt of claim 46, furthercomprising at least one from the group consisting of thermoplasticelastomeric and plastomeric polymers, polyphosphoric acid,anti-stripping additives, warm mix additives, emulsifier, and fibers.48.-56. (canceled)